In situ formation and dispersion of lanthanide complexes in wormlike micelles

Lanthanide-containing, water-based fluids normally suffer from low photoluminescent (PL) and/or colloidal stability, which greatly hinders their applications. Herein, we report the preparation of PL fluids which contain in situ formed europium complexes in aqueous solution. The strategy first relies on the construction of wormlike micelles by mixing a zwitterionic surfactant (tetradecyldimethylaminoxide, C₁₄DMAO) and a tridentate ligand for a lanthanide cation (2,6-dipicolinic acid, DPA) in water. The addition of the dual-functionalized DPA to an aqueous solution of C₁₄DMAO (100 mol L^-1) induced non-monotonic rheological changes, with the expected formation of a pseudogemini surfactant at a DPA-to-C₁₄DMAO molar ratio of approximately 1 : 2. When a third component of EuCl₃ is introduced to this system, complexes formed in situ between Eu³⁺ and DPA, resulting in bright red-emission. Besides DPA, C₁₄DMAO is also involved in the complexation, which squeezes out water molecules and greatly improves the PL stability of the fluid. The synergetic effect among Eu³⁺, DPA and C₁₄DMAO leads to the high colloidal stability of the fluid, opening the door for a wide range of potential applications. Further tests indicate that this strategy can be easily expanded to other lanthanide cations such as Tb³⁺.